Preparation of hydrogel catalyst



patented '10, 1950 The presentinvention is concerned'withla proc- .ess for they manufacture of improved catalysts. The invention is more particularly concerned with an improved process for the production of" true hydrog'els as compared to gelatinous precipitates. In accordance with my invention non- Vsiliceousjtrue hydrogels'of inorganicoxides are produced by. treating i ametallic .salt solutionl with magnesa. Y l

It is well known'i'n the art tolimprove the quality` of oils.,particularly` petroleum foils; vby treatingthe same with catalystsl uncle;` various operating conditions; For example, it is knownto treat high-boiling petroleum oils with a catalyst' comprising silicia f at temperatures `in "the range from `about 6001F. to about l100 Fwin orderto crackthe oil and towsecure-petroleum oil fractions boiling in the motor fuel boiling range.2 x-l ides of other metals, as for example, magnesium, manganese, zirconium, beryllium `and aluminum are employed in conjunction with the silicaf A particularly desirable catalyst suitable for treating petroleum oils boiling inthegas-oil boiling range in order. to produce lowerboiling fractions comprises a silica-alumina catalyst.' u

Heretofore, thesel hydrogel silica catalystslhave `been preparedby various procedures; i One Amethod is to prepare the silica hydrogel by mixing an alkali silicatewith an acid; usually comprises asodium silicate j Y Si,igiirslosgzs sijaf. "'ijl solution having' f a specific) gravity jsf] peut `,1,2.

This 'is mixedwiih a 'sulfuric acid havingfaisses cie gravity Ycfabbut `1:19. The hydrosol maybe impregnatedfwith' a soluble `salt of' the desired metal or'the'hydrosolmay beallowed tol gel and the resulting hydrogel washed and soaked ina solution comprising the salt of the desired metal-` or metals. Qnemethod employed for 'the preparation of` a silica-magnesl'a catalyst is lto prepare the hydrogel by the miijzingk ofia silicate and sulfuric scid." lThe hydrgeiis washed and mixed and granulated" with magnesia' and watergf The mixture is "passedA througha :colloid y'n'iillfjand homogenized. The catalystffisfaged at room temperature `for a `period(from'` about 24 vto l72 hours.` Elevatedtemperatures' have been" em-l ployed inl which casesy the aging time period is reducedjto from about to hours". The catalyst' is dried at atemperature inthe range from li'zed *for the preparation the silica-,magnesia The alkali' silicate 1 .2524189.91 '}r1tEPA1tAfrroN 10F HYDRoencATALYsT fohsrles xihitelinafntii' Rigfilalf "signor to I StahdardilDevelopment Compa a '"a corporation offDelawar-e n "l i .NoiDrawr vf 'r- Applicatinngliiovemiierfz;194s,

`Trie.sha1shearsmais snaren to yprecipitate the magnesla.; This" maj/iv require 1 ajtime periodof from' about 8` to'` 10 hours'.V Ajpre- 1 terred method of `preparing va'r.-.`ata1yst kcomprising silicaand magnesia is to addV magnesia. to al silica y hydrosol orto a silica hydrosol impregnated with ia metal salt, 'such as with lan aluminum salt; The

mixture is washed preferably at elevated temperatures. The general process comprises adding magnesia preferably asalslurry in lwaterA to a lsilica hyciroscl` which has been impregnated with a salt, as .forexample with an aluminum salt. The action of magnesiais to neutralize the free acid. thus causing rapid,k setting of the" hydrosol to the hydrog'el and also to'decompose the aluminum salt or other salt present causing pre- "cipit'ation' 'of alumina within and throughoutthe gel. QExcess magnesiaY used ,over theserequirements remains in thennished product as .niagnesia.

't l yMy process isl particularlydirected toward the preparation of true nonsiliceous hydrogels, as

compared to gelatinous precipitates, oft'inorganic oxides. True v`hydrogels may be: dened fas precipitates which occupy the entire volume of the solution from which' they are `formed,`and possess 'a d'eiinitely rigid structure i and when fractured will fshow a conchoidalf fracture as lcompared to 'an irregular and ragged' edge fracture. O'nthe 'other' hand, l g'elatinous` precipitates occupy'fonly j a" part of tlieqvolume ofthe solution froml `which theyfarewformed andhave'nof'rigidity 0f struc- "the other hand; beth' hydrogels andgelatinous y`precipitai-,e's' can usuauy'he anelito sends which havel a' gel structure. However', for manypur- I poses; such as adsorptivefagentsor catalysts or catalytic carriers, theft'ru'ev hydrogelsz'show dis- "tinct advantages since the dried gel prepared from the true hydrogels usually possesses a more open and porousfstructure as compared to the gels producedirom gelatinous precipitates. Furthermore, the hydrogels'" can" be more easily washed -free of soluble impurities due `to the tendy encyof the gelatinous precipitates to peptizeupontwashing.` Aldistinct .andjfurther advantage of hydrogen ischst dus to the 'rigid structirefihy catalyst is to prepare thesilica hydrogel bymix-"- ing sulfuric acid and an alkali metal silicate.

can beiormedinto high qualit? ,Slhere's..A

'have beene'mployedlfor the. preparation ofhydro- `gels with which' thejpresnt invention isconcerned. For example; ari alumina hydrogel has been produced by the treatment of a peptized is dissolved in water.

alumina sol with a weak acid or base. Another method used for the preparation of hydrogels of the type with which the present invention is concerned is to add ethylene oxide, propylene oxide, or an equivalent oxide to a metallic salt solution. This is an old and well known method and the hydrogels produced are of excellent quality. This process, however, has the disadvantage that it is limited to halide starting ma.- terials, the reagents are expensive, poisonous, highly inflammable and diiilcult to handle. For example, ethylene oxide is a gas and propylene oxide is a volatile liquid, the usefulness of which is limited by its low solubility in salt solutions. Furthermore, the product of the reaction, ethylene chlorohydrln is poisonous.

Another method heretofore employed for the preparation of hydrogels is` to add hexamethylenetetramine to a metallic salt solution. Although this method also produces satisfactory hydrogels, it cannot be used for example in the preparation of desirable hydrogels, as for example alumina hydrogel. Furthermore, the method is expensive since it involves a wastage of one and one-half mols of formaldehyde for each equivalent weight of oxide formed by means of hexamethylenetetramine. Furthermore, the formation of by-product formaldehyde is not desirable. y

As stated heretofore, I have now discovered that true hydrogels of inorganic oxides may be readily prepared by treating a metallic salt solution with magnesia. The oxides may be oxides of metals of groups I, II, IV, VI and VIII of the periodic table. Suitable oxides are, for example, hydrous oxides of aluminum, chromium, titanium, iron, tin, thorium and zirconium.

The method of preparation is to start with a water soluble salt of the metals. These metals, as stated heretofore, are preferably selected from groups III, IV, VI and VIH of the periodic table. The salts generally comprise the chlorides, the sulfates and the nitrates. Satisfactory salts are, for example, aluminum chloride, aluminum sulfate, aluminum nitrate, chromium chloride, chromium sulfate, chromium nitrate, iron sulfate, zirconium nitrate, tin chloride, thorium nitrate and the like.

The'waterl soluble salt of the satisfactory metals u It is preferred that the salt solution be relatively concentrated and preferably vthat the concentration be at least 80% of the saturation value. A water slurry of magnesia is prepared and the magnesia slurry mixed with the salt solution. In general it is preferred that the concentration of the salt solution should be such that the product will contain at least 50 grams of theA metal oxide per liter. If too low a concentrationis employed there results a hydrosol of the hydrous oxide which can be freed of soluble magnesium salts by dialysis.

The following reactions serve to illustrate my invention:

The hydrogels formed in accordance with my process may be washed free of soluble magnesium salts either before or after drying. Also, although it is preferred to employ a water slurry of magnesia, dry'magnesia powder may be introduced per se into the salt solution. The magnesia can be used eitherin stoichiometrical quantity or in larger quantities provided free magnesia in the final product is not objectionable. On the other hand, if excess magnesia has been used, the excess can subsequently be removed by treating the hydrogel or the dried gel with ammonium chloride or other weakly acidic solutions.

The time required for the hydrogel to form depends upon various factors. The time of set will be dependent on operating conditions, such as the nature of the salt used as a starting material, the concentration of the salt employed, the temperature of the set (high temperature favoring more rapid setting), and the quantity of magnesia employed. The time of setting will also vary, depending upon the quality of magnesia used. 'I'he following tabulation lists the results of operations in which ccs. oi' a 1 M A12 SO4)3 solution was treated at room tempera.- tures with a slurry of 12 grams of 200 mesh magnesia in 40 ccs. of water.

Type of magnesia Set time, seconds A 360 B 10 C The foregoing magnesias differ in the temperature at which they were calcined, the higher temperature of calcination resulting in the longer set time. The temperature of calcination is in the range from about 700 F. to 2000" F.

Certain hydrous oxides cannot be formed as hydrogels by my process, as for example oxides of copper, cobalt and zinc. drous oxides can be made a substantial part of a true hydrogel by mixing the salt solution with the salt of a metal which readily forms a hydrogel before treatment with magnesia. By this process it is possible to produce a hydrogel of composition (dry basis) ZnAlzO4 which serves as a useful support for certain reforming or hydroforming catalysts.

The temperature I prefer to use in the treatment of the salt solution with magnesia is in the range from about 50 F. to 200 F. A particularly desirable process for rapidly producing hydrogels is to treat the salt solution with magnesia at a temperature in the range from about 125i F. to 200 F., particularly at about 150 F.

Although I do not wish to limit my invention by the mechanism of the reaction, I consider the mechanism of hydrogel formation when mag.- nesia is added to a salt solution to be as follows:

Magnesia when added to an acidic solution, due to its low rate of solubility, gradually raises the pH throughout the solution without localized regions of high pH such as are unavoidable when using more soluble bases. This condition is ideal for the formation of true hydrogels.' On the other hand, the localized regions of high pH obtained when treating a salt solution with a more solubley base are favorable to the formation of gelatinous precipitates. Magnesia is the preferred reagent, but other diiiicultly soluble bases such as the alkaline earth carbonates, silver or lead oxide. etc., might be useful under special circumstances. For example, I have prepared a true hydrogel of alumina by treating a solution of aluminum chloride with the stoichiometric amount of powdered calcium carbonate. However, this hydrogel suffered the disadvantage of being full of bubbles due to the carbon dioxide released by the reaction.

I wish to emphasize that my invention is par- However, Athese hy- In orderto further illustrate my invention, the following examples are given:

Examples 1 A slurry of 12.0 g. of MgO in cc. H2O was added with stirring to cc. of 1 M A12(SO4)3 solution at room temperature. The mixture was stirred for seconds at the end of which time it set suddenly to a rm hydrogel. The latter was aged overnight, washed free of magnesium sulphate with distilled water, and dried to an alumina gel of high quality.

Example 2 Example 3 To 100 cc. of a stirred solution of 6 N AlCl: at

room temperature was added a slurry of 24 g. MgO

in 40 cc. of H2O. Within 6 minutes, the mixture set toa iirm hydrogel of alumina which contained a considerable excess of magnesia.

Example 4 To a stirred solution of 72 cc. of 1 M A12(S04)3 and 28 cc. of 2.59 M ZnSOi at room temprature was'added a slurry of 11.6 g. MgO in 40 cc. H2O. The mixture set to a rm hydrogel in 75 seconds.

Example 5 The hydrogel of Example 4 was produced in the form of spheres by permitting the mixture to set while descending a rcolumn of lubricating oil in the form of drops. 'Ihe hydrogel was aged overnight, washed `in distilled water, and dried slowly by heating to about F. in a moist atmosphere. The dried gel beads were heated to 1000 F.

Example 6 A slurry of 20 g. MgO in 40 cc. H2O was added with stirring to 100 cc. of 7.5 N Cr(NO3) s at room temperature. After 500 seconds, the mixture set to a firm hydrogel. The later was aged overnight, washed, and dried to give an excellent dry vgel of chromia, which still, however, contained some magnesia due to the excess magnesia used.

A slurry of 24 g. MgO in 40 cc. H20 was added with stirring to 100 cc. 6 N FeCl: at room temperature. The mixture set to a hydrogel after seconds.

Example 8 A slurry of 8 g. MgO in 40 cc. H2O was added with stirring to 100 cc. of 1 M SnCl4. ture set to a hydrogel in 22 seconds.

Example 9 A slurry of 12 g. MgO in 40 cc. H2O was added with stirring to 100 cc. 1.5 M TiC14. The mixture set to a hydrogel in 10 seconds.

The process of my invention is not to be limited by any theory as to mode of operation, butv only in and by the following claims.

1. An improved process for the preparation of true hydrogels which consists essentially in preparing an aqueous solution of a soluble salt of a metal selected from the group consisting of aluminum, chromium and iron in amount suiiicient to produce a concentration in the product of at least 50 g. of metal oxide per liter and adding to the said solution' at least a stoichiometrically equivalent amount of magnesia to form a true hy drogel of the said metal.

2. The process deiined b'y claim 1 wherein the soluble salt of the metal selected is an aluminum salt.

3. The process defined by claim 1 wherein the soluble salt of the' metal selected is a chromium salt.

4. The process dened by claim 1 wherein the soluble salt of the metal selected is an iron salt.-

5. The process as set forth in claim 1 wherein a mixture of soluble salts is used to produce the y indicated metal oxide concentration in the prod- REFERENCES CITED The following references are of record in th file of this patent:

UNITED STATES PATENTS Number Name Date..

2,156,903 Ruthru May 2, 1939 2,255,607 Ayers et al Sept. 9, 1941 2,383,643 Fulton et al. Aug. 28, 1945 2,408,146 l Kearby Sept. 24, 1946 2,412,958 Bates et al. Dec. 24, 1946 FOREIGN PATENTS 00 .Number Country Date Great Britain May 22., 1933 The mix- 

1. AN IMPROVED PROCESS FOR THE PREPARATION OF TRUE HYDROGELS WHICH CONSISTS ESSENTIALLY IN PREPARING AN AQUEOUS SOLUTION OF A SOLUBLE SALT OF A METAL SELECTDED FROM THE GROUP CONSISTING OF ALUMINUM, CHROMIUM AND IRON IN AMOUNT SUFFICIENT TO PRODUCE A CONCENTRATION IN THE PRODUCT OF AT LEAST 50 G. OF METAL OXIDE PER LITER AND ADDING TO THE SAID SOLUTION AT LEAST A STOICHIOMETRICALLY EQUIVALENT AMOUNT OF MAGNESIA TO FORM A TRUE HYDROGEL OF THE SAID METAL. 